Metallo organo derivative



I characteristics but new properties;

Patented Feb. 3, i942 UNITED STATES PATENT OFFICE 2,272,133 METALLO ORGANO DERIVATIVE Sol Shappirlo,"Washington, D. C.

No Drawing. Application October 24, 1938, Serial No. 236,785

G CIaims. (01252-49) f Among the objects of the present invention is.

the production of motor fuels or other hydrocar bon distillates and fractions, such as lubricating oils, which contain novel types of metallo'organo. derivatives, widely, departing fromthe metallo 7 aryls and alkyls of the prior art,'and giving to such products as motor fuels, not only improved Still further objects and-advantages'will appear 1 from the more detailed description set forth below, it being understood however that such more detailed description is'given by way of illustration and explanation only, and not by way of limitation, since various changesiherein may be made by those skilled in the art, without de-' parting from the scope and spirit of the present invention. L

In accordance with the present .invention, me-' tallo organocompounds are produced in which propylene or acetylene, a current of. said gas may be passed through the. liquid metallo organicv or .a solution of-the metallo aryl or alkyl, either in a solvent therefor or in the motor fuel or other hydrocarbon distillate. Where the unsaturate is a liquid or solid, such as cyclo pentadiene, for example, the liquid or solid may be added to the solution containing the metallo alkyl or aryl,

or the latter may be dissolved in the liquid unsaturate. The reactions involving the gaseous unsaturates, such asethylene, propylene and acetylene, may be carried out at ordinary room temperatures and pressures, the gases being well dried to removeany moisture.

mospheric pressures may be used.

e processwill beexemplified by'the treat-' ment of lead tetraethyl and Grignards,a such-as ethyl magnesium chloride .(or other halide) ,with

the gaseous unsaturates, it being understoodth'at such illustrative reactions are exemplary .of the use ofother types of metallo organics.

Thus, a well dried current of acetylene bromide (prepared in the usual way) at ordinary temperatures, until the extent of reaction desiredhas taken place.: The maximum conversion is.

reached after about twenty-four hours. The

-. acetylenic magnesium bromide is produced;to-

the organic radicle contains anunsaturated link- 5? age, such as the oleflnic C -C- orthe acetylenic CE'C- the organic radicles containing such groups being of any desired character, such Patent 2,012,356, page 3, lines 3-25. Thus lead asaliphaflc or acyclic, aromatic or isocyclic, heter-v ocyclic, etc., and the metallo component being.

any desiredn'ietal, but preferably one of the 40 metals and non-metals of accepted use for antidetonants in motor fuels, such as lead, tin, antimony, zinc, phosphorus, silicon, arsenic, mercury and thallium-etc.

In, producing these modified-motor fuels, for example, various methods arev available, but the simplest is that in'which the motor fuel'or other lead acetylenic' derivative is formed toge her'with gether with ethane. "I'he' Grignard mayberecovend and used for organic synthesis, or'itm'aybe addedv to motor fuel. It may be converted into any of the other .metallo acetylenic derivatives by double decomposition in the usual way. See

a'cetylenic derivatives maybe produced and added v to motor fuels.;.

Or the lead tetr'iiethyl insolution inany 'desired solvent is treated with a current. of well dried acetylene atordinary temperat res. vThe ethane.

acetylene to give the corresponding zinc'acetylene derivative, ethane beingformed at the same time.

hydrocarbon'fraction containing the-metallo aryl or alkyl, is reacted with the desired unsaturated compound under conditions wherein the unsaturated compound forms a radicle containing the. 'olefinic or 'acetylenic linkage, and the latter replaces the saturated alkyl or aryl group of the original metallo organo compound, producing, new types of metallo organics. Where In an analogous, ,way the olefinic derivatives"? v may be producedof the Grignards, of lead, -zinc,

' hydrocarbon fractions and jdistillates.

Toexemplify the production of an olefinicmev tallic derivative, 9. liquid oleflne will sufllce. One v m'olecularweight of ethyl magnesium bromide the unsaturated reactant is a gaslike ethylene, is prepared i'n-the'usual way. Cyclopentadiene Higher temperatures and superatmospheric pressures may be used; particularly where ,unsaturate liquids are beingtreated; 'while even low'tem'peratures and suba't v passedthrough the'ethereal solution of ethyl magnesium Similarly zinc 'diethyl may be. treated'w ith (113) is maintained at the boiling point, and the ethyl magnesium bromide introduced. The reaction takesabout 12 hours for completion. Cy-

reaction is more rapid, being completed in or 6 hours at 60 C. The process can be further improved by using ligroin (boiling 60 to 80 C.) as the medium, and dissolving the cyclopentadien therein and reacting with the Grignard. Even though the latter is not soluble in the lig-roin, by the use of agitation, the reaction is very rapid, andis completed in 3 hours at temperatures of 45 to 50 C.

Other unsaturated compounds, such as indene and fiuorene, may be used to give corresponding Grignard type reaction products. Or as pointed out above, the metallo alkyls, for example, may be similarly treated with these various olefinic materials to give corresponding metallo olefinic compounds.

Many ofthese metallo derivatives are new compounds including, for example, the lead acetyl- J mid and olefinic derivatives, the Grignard olefinic derivatives of ethylene and propylene, etc.

They are desirably used herein in motor fuels,

lubricating oils, etc., but may be used in organic v syntheses of far reaching importance.

While the preparation of these metallo organics has been illustrated above in the production of individual organic compounds, more desirably they are produced in situ in the motor fuel, for example. In such cases, complex mixtures of metallo derivatives are produced, and at the same time the hydrocarbons which are formed, favorably affect the motor fuel as, for example, in octane number. In producing, such products in situ, the Grlgnards or metallo aryls may be produced in situ in the motor fuels for example by any desired method, as for example the methods described in U. S. Patents 2,012,356 and 1,974,167. In such cases, the motor fuel or other hydrocarbon fraction contains complex mixtures of metallo organo derivatives, such as, for example, various lead alkyls which will. include leadbutyls, lead pentyls, lead hexyls, etc. Such complex organo derivatives of the metal, when treated with the unsaturate yields lead derivatives of the unsaturate, such as lead ethylenic or lead propylenicor lead acetylenic, etc. derivatives, while higher hydrocarbons are formed. The latter raise the octane number of the motor fuel, while the metallo derivatives act as antioxidants. For example, a well dried stream of acetylene is passed through a motor fuel containing lead alkyls produced in situ, normal temperatures being employed, and the reaction being continued for six hours. Lead acetyl ide is formed, together with paraflln hydrocarbons. The alkyl radicles set free in nascent con dition recombine in various ways.

Analogously, a gasoline containing a complex mixture of Grignards produced in accordance with Patent 2,012,356 is treated at 40-70 C. with a current of ethylene for three to six hours. The

corresponding magnesium ethylene halide is produced, together with paramns of various types.-

In lieu of using pure gaseous unsaturates, gaseto the production of the olefinic plumbanes and other metallo organics, Thus, in one case, the

gas from a vapor phase cracking plant contained 6% of butylenes, 17% propylene, 27% ethylene and 50% methane. It is desirably employed to treat a complex lead alkyl motor fuel produced in situ by the methods of Patent 2,012,356. The

gas is run through the motor fuelat a temperature of from 20-'-50 C., and if desired some pressure may be used, as for example, about 90#/|:l". The current of gas is run through for five hours to produce the conversion. More desirably coun-' ter current contact of gas with liquid is utilized,

and with slightly elevated temperatures and pressures, the process of conversion lsquite rapid. By the'use .of still gases, vapor phase cracking gases, etc., utility is made. of products readily available in the refinery. Very complex mixt'ures of metallo ethenyls, propenyls, butenyls,

etc. are produced.

Where polymerization of the unsaturates takes place, the motor'fuels may be redistilled. But the conditions of reaction can be chosen to avoid so extensive polymerization as to require distillation. 4

While ,motor fuel fractions, such as gasoline, have been particularly mentioned, other hydrocarbon fractions and distillates may be similarly treated. For example, a lubricating oil used for cylinder lubrication may be given a complement of the lead organics. treated. The ethylene, propylene, etc. are illustrative of the class of olefinic materials, while acetylene illustrates the class of compounds containing the -CEC group. The term olefinyl" like the term -'ethylenyl and similar terms is ous mixtures containing the unsaturates may be employed. Gases from cracking units may thus be used, since they contain relatively high conintended to cover compounds in which the metal is joined directly to carbon of olefin group such as ethylene, etc. Furthermore, the term "metal is used herein to cover both metals and nonmetals of the character set forth abovewhich are found to be useful in motor fuels in connection with anti-detonating and other types of metal derivatives.

Or Diesel fuels may be so The desired derivatives may also be produced by reaction of alloys and amalgams, particularly,,

of the alkali metals, with halogen derivatives of the unsaturated hydrocarbons. Thus sodium lead alloy may be reacted with ethenyl chloride (CH2=CHC1) to produce the corresponding lead derivative. Such reactions may be carried out in any desired medium or vehicle as in the presence of the gasoline or other hydrocarbon vehicle. The processes given above in which alkyl or aryl groups of metallo alkyls or aryls are replaced by unsaturated organic radicles are illustrative of the wide variety of processes which can be utilized to modify the metallo organo ingredients of motor fuels, lubricating oils, etc., by simple means in view of the great reactivity of the metallo organic derivatives such as lead alkyl, zinc alkyl, the Grignard reagents, etc. Processes can further be employed to modify the ingredients along other lines; and to introduce either other substituent groups, or partially to replace alkyls or 'alkylene groups in such metal derivatives. a

An important process in this connection is that in which an organic derivative containing a or partially by nitrogen containing radlcles, in

tents of olefines, and may be directly applied which the nitrogen is directly attached'to the metal. As a result amides or amido derivatives responding metal derivatives, either completely containing no alkyl or aryl or other radicles, ex-

ce t those which may be attached to the nitrogen. A wide variety of different typ s of compounds can thus be produced, and by control of the processes, mixtures of complex substances of the character can all be produced simultaneously by isimplehnreans in the motor fuels themselves, and preferably are so produced. While these reactions can be carried out utilizing individual compounds, the simplicity of reactions by which the metal derivatives are treated in the motor fuels themselves, particularly when they have been produced in situtherein along lines indicated above, make such methods preferable to others. Various of these processes are illustrated below.

It should be kept in mind in this connection that where the metal derivative is, being treated in situ in a motor fuel, hydrocarbon oil, etc., that such metallo organo derivative may be present in a concentrated degree in such vehicle, and after the modification of the metallo derivatlve, the resulting material containing a concentration of the new metallo derivative may be diluted with motor fuels, gasolines, etc., of any desired type, to reduce the content of metal derivative to the small amount required, such as only a fraction of a percent in the final commercial product.

For example, a motor fuel fraction containing lead alkyls produced in situ in such motor fuel by the methods set forth in Patent 2,012,356, is subjected to treatment with ammonia by passing a dry current of ammonia into the motor fuel containing the metallo alkyls and aryls. The process can be carried out at ordinary temperatures and under ordinary pressures, but if desired the reaction mediums can be heated to moderate temperatures and superatmospheric pressures can be employed. Counter-current methods can be utilized for contact of the gas with the liquid here as in other cases illustrated above. As a result of such treatment, depending on the extent to which the replacement is permitted to occur, that is the length of time treatment, there is produced as an ultimate derivative lead amide, in which the metal is directly attached to the nitrogen of the amido group. If the reaction, however, is interrupted before complete displacement of the alkyls and aryls by the amido group, mixed compounds represented by the amido metallo alkyls'or amido metallo aryls are obtained.

If it is desired to treat the metallo alkyls or aryls individually, and subsequently to add the produced products to motor fuels or other compositions, an analogous process may be employed. Thus a current of well dried ammonia is led into an ether solution of zinc ethyl under conditions analogous to those described immediately above with the production of zinc amide.

Similarly hydrazin may be employed to produce corresponding metal hydrazides. For example, hydrazine vapor is passed into the solutions containing the desired metallo organic derivative to the small amount required, such as plained above. Onsuch treatment of a solution contaning a lead alkyl, for example, the hydrocarbon corresponding to the alkyl present is liberated, and the metal hydrazide is produced, in which event, in this instance, lead hydrazide would be obtained. Here too, the reaction may be interrupted before the complete replacement of alkyl or aryl groups as obtained by means of the hydrazide radicle, so that mixed hydrazide metallo 'alkyls or hydrazide metallo aryls are obtained.-

Analogously, the lead ethylenyl, and other metallo organic derivatives. produced as set forth above, which contain an unsaturated group, and in which the metal is joined directly to the carbon, may be treated with ammonia, hydrazin, or other nitrogen containing bases to obtain displacement, either completely or .in part of the carbon-containing radlclesby the nitrogen-containing group.

In lieu ofuslng ammonia, hydrazin, or similar types of compounds, the substituted ammonias and hydrazines may also be employed. Thus any of the amines, particularly the primary and secondary amines may be employed for reaction with the metallo derivatives of organic radicles to produce substituted compounds in which the metal is attached to the nitrogen ofthe amino radicle. Where the amines employed are gaseous or easily vaporized, as in the case of methylamine,

1 carbon.

ethylamine, etc., the gaseous amine may be conducted into the solution containing the metallo aryl, alkyl or analogous compound at ordinary temperatures, the reaction readily taking place, and producing corresponding metallo derivatives in which the metal is joined to the nitrogen of the amino group producing an alkyl amino metal derivative. Again, if the reaction is not permitted to go to completion, the substitution is effected in part only with. theresult that mixed derivatives, corresponding to alkyl or aryl, amido metallo alkyls or aryls are obtained. Where the amines are liquids and not readily vaporized, they may be utilized in liquid condition for reaction with the solution, such as the gasoline solution of the metal alkyls, etc.

By the methods set forth above, therefore, motor fuels and other hydrocarbon vehicles carrying metallo derivatives of carbon and nitrogen containing radicles are readily produced, most desirably in situ in the motor fuel, lubricating oil, or similar fractions with which they are to be employed. Metallo derivatives of unsaturated organic compounds in which the metal is joined directly to the carbon, ormetallo organic derivatives, including nitrogen-containing radicles, in which the metal is attached directly to the nitrogen, or combinationsof such materials are readily produced in the motor fuels, etc., or may be produced externally of the motor fuel, for example, and subsequently added thereto. These various metallo derivatives are of great importance in the modification of motor fuels giving them new'properties, particularly as anti-detonating agents, anti-gumming compounds. etc.

Having thus set forth my invention, I claim:

1. A lubricating oil of hydrocarbon typecone taming a metal compound of an organic compound containing an unsaturated aliphatic radicle in which the metal is joined directly to 2. A composition of matter comprising a hydrocarbon lubricating oil containing a metallo organic compound, the metal constituent of said compound being directly joined to a carbon atom of an alkylene group and being selected from a metal from the group consisting oi mercury, zinc, thallium, antimony and arsenic. 3.-A composition of matter comprising a hydrocarbon lubricating. oil containing a lead organic compound, the lead constituent of said compound being directly joined to a carbon atom of an alkylene group. a 4. A composition of matter comprising a hydrocarbon lubricating oil containing an organic from the group compound of an element selected consisting of lead, tin, antimony, zinc, phosphorus. silicon, arsenic. mercury and thallium, the said selected element being directly Joined to a carbon atom or an alkyle'ne group.

5. A composition of matter comprising a hydrocarbon lubricating oil containing an antimony organic compound, the antimony constituent or said compound being atom of an alkylene group.

8. A composition of matter comprising a hydrocarbon lubricating oil containing a mercury organic'compound, the mercury constituent of said compound being directly Joined to a carbon atom of an alkylene group.

' SOL SHAPPIRIO.

rectly Joined to a carbon 

